JPH0561290B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to novel polyquaternary ammonium polymers and cosmetic compositions containing such polymers. The polymers according to the invention can be used advantageously, for example, in the preparation of scale inhibitors, flocculants, hair/skin conditioning agents, etc. [Prior Art] Christiansen's US Pat. No. 4,157,388
Polyquaternary ammonium compounds are described for use as antistatic agents and humectants in hair conditioners and fibrous textile products. These compounds are generally liquid at room temperature. Mirapol A-15 has the formula: One compound according to the Christjansen example having the formula: where n is at least 1. The polyquaternary ammonium polymers of the present invention are found to be easy to handle, as they generally do not require any special order of addition and can be added into the oil or water phase, as detailed below. Ta. It has also been found that the polymers of the present invention generally have better water solubility than the Christjansen compounds described above. SUMMARY OF THE INVENTION In one aspect, the invention resides in a polyquaternary ammonium polymer having a number average molecular weight of at least 20,000. formula: In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and are hydrogen, methyl, ethyl, propyl, -CH ₂ CH ₂ OH, -CH ₂ CH(OH)CH ₃ ,
and _-CH2CH2 ( _{OCH2CH2 ) pOH} , where p is 0 or an integer from 1 to 6, and _R1 , _R2 , _R3 , and _{R4 are} cannot represent hydrogen at the same time; x and y may be the same or different and are integers from 1 to 6; n is the number of repeating units; m is an integer from 1 to 34; and Z is a halogen or an amino-diamidammonium residue of the formula: , where R ₁ , R ₂ , R ₃ , R ₄ , and m are the same as above. In addition, as a preferable embodiment, m in the formula is 4 and x is 3. Another aspect of the invention is a cosmetic composition comprising a suitable cosmetic carrier and a polyquaternary ammonium polymer as shown in the above formula. Some preferred embodiments of the cosmetic composition of the present invention are as follows: (1) A composition in which m is 4 or 7, and x and y are each 3. (2) A composition in which the cosmetic carrier is a carrier for use in hair formulations. (3) A composition in which the hair preparation is shampoo. (4) A composition in which the cosmetic carrier is a carrier for use in skin care products. (5) A composition in which the skin care product is a soap. DETAILS OF THE INVENTION Applications of the polymers of the invention include, for example, use in hair care and skin care compositions such as shampoos, soaps and lotions, and as anti-scaling and flocculants, and have significant conditioning properties. Used as a softening agent and softening agent. The polyquaternary ammonium polymer of the present invention is represented by formula (I) as described above. The polyquaternary ammonium polymer of the present invention is
It can be prepared by condensing a polyamine and a quaternizing agent X-A-X as follows: The polyamine used in the above condensation reaction is 2
It is produced by the condensation of various diamino compounds and dicarboxylic acids. The diamino compound has the formula:

[expression] and

〔Example〕

Example I A A reaction flask was charged with 438 g (3 moles) of adipic acid. After heating to approximately 55℃, 612g (6 moles)
of dimethylamino-propylamine was added in about 5 minutes. During this addition the temperature rose to 101°C. The reaction mixture was heated to 165-170°C for about 3 to 4 hours. Distillation began at approximately 147°C. 165
After reaching a temperature of 0.degree. C., 62 g of dimethylamino-propylamine (DMAPA) was added over half an hour. Then the reaction mixture was heated to 180
It was heated to 185°C for about 2 hours. After reaching a temperature of 180°C, 62g of DMAPA was added in about half an hour and the temperature was held at 180-185°C for half an hour. Apply vacuum and gradually increase to 5-10 mm to remove water and excess
DMAPA was removed. A 5-10 mm vacuum was maintained at 180-185°C for 1 hour. The reaction mixture was cooled to 100°C, the degree of vacuum was lowered, and the adipic acid condensate was recovered. The above reaction was carried out by combining adipic acid with (1) an equimolar amount of azelaic acid or (2) an equimolar amount of dimer acid HOOC.
Repeated by substituting -( _CH2 ) ₃₄ -COOH. In the reaction flask of B2, 282.73 g (0.88 mol) of the adipic acid condensate formed in Example A above and water were added.
152.24g and the mixture was heated to 90°C.
122.28 g (0.855 mol) dichloroethyl ether was added over a period of 4 hours while maintaining a temperature of 90-100°C. After the addition was complete, the reactants were heated to 100°C and held at about 100°C for 5 hours.
Analysis of chloride ion shows that the reaction is 99.7%
I found out that it was completed. 115.8 g of water was added to the amber material and the mixture was heated to distill off 51.4 g of distillate to remove traces of unreacted dichloroethyl ether.
The final product was a clear amber liquid. Ten
% aqueous solution was 8.32. The solids content was 68.2% by Karl Fischer measurement (31.8% water) (American Oil
As described by the Chemistry Society). This compound has an intrinsic viscosity average molecular weight w of 52500.
Determined from n (number average molecular weight) of 45800,
It was found to have an n value of approximately 115. EXAMPLE Reaction B above is repeated by substituting the product of Example A with azelaic acid instead of adipic acid for later use in conditioning shampoo C. of the azelaic acid-derived product of the present invention. Example (Reference example) The above reaction B was carried out using 1 dichloroethyl ether,
Repeated by substituting 6-dichloro-hexane. Examples (Reference Example) Azelaic acid derivatives were prepared by reacting azelaic acid condensate with 1,6-dichloro-hexane. EXAMPLES Polyquaternaries according to the invention were evaluated for use as conditioners in hair and skin care products. Four formulations were created with the following ingredients:

[Table] Sodium

[Table] Each formulation was adjusted to pH 7.0. Milatein CB is cocoamidopropyl betaine and is a high foaming agent as well as a viscosity increasing agent. Milanol C2M concentrate is a viscous, clear amphoteric surfactant solution derived from coconut fatty acids, specifically the dicarboxymethylated derivative of cocoimidazoline. Mirapol A-15 is a hair and skin conditioner as described in US Pat. No. 4,157,388. These four formulations were evaluated by hair swatch testing for wet and dry combing results, antistatic effect, softness, shine, etc. It has been found that formulations B and C perform better than formulation A in terms of conditioning ability, ie manageability and combing of the hair when wet and dry. Formulation C was found to be slightly better than Formulation B.

[Table] Milanol 2MCAS-MOD is a one-eye irrating combination of lauryl sulfate and laureth-3 sulfate, a dicarboxymethylated derivative of cocoimidazoline.
It is a mixture with properties. Milatein CBS is cocoamidopropyl hydroxysultaine. Each formulation was adjusted to pH 7.0. The same evaluation as above was performed on hair swatches.
Formulation C was found to be the best here, and Formulation B the next best.

[Table] Each formulation was adjusted to pH 7.0. Sedepar TD404M is trideceth
It is sodium sulfate. Superamide GR is coco diethanolamide. Mercuat 550 is a cationic polymer. Glidant is a preservative. After washing their hands with these five formulations, five panelists chose Formulation C as the best in terms of after feel, Formulation B as the next best, and Formulation D as the best. It was somewhat hazy.

[Table] These formulations were adjusted to pH 5.5. The four formulations described above were evaluated for use as gloss activators and pre-style lotions to determine increases in gloss and setting. Five panelists selected formulation C as the best;
Formulation B was chosen as the next best.

【table】

Table: Prototype C was selected as the best in skin softening and conditioning. Prototype B was the next best. The novel polyquaternary ammonium polymers of the present invention were evaluated for use as antistatic agents in hair care products. Eight formulations were created with the following ingredients:

【table】

[Table] *Used at 1% based on active ingredients. Examples and Examples are reference examples.
Hair swatches were soaked in a 25% solution of the above formulation for half an hour and rinsed with 40°C water for 1 minute. Hair swatches were dried overnight at ambient temperature and antistatic properties were evaluated by measuring static charge with an electrostatic electrometer (Keithley Model 610C). Formulation D exhibited the lowest static charge of the eight formulations. There were no significant differences in the values obtained for the other formulations. Example (a) A formulation having the following composition was prepared.

[Table] Yes.
Mirapol A-15 is a quaternary polyurea product according to Christiansen, US Pat. No. 4,157,388. This structural formula is shown on page 5 of this specification. Mercuat 100 is a high molecular weight dimethyl dialkyl ammonium chloride polymer. The test formulations were made by heating Group I and the Group ingredients separately to 75° C. and then adding the mixture to Mixture I with stirring to homogenize the mixture. Then, citric acid was added to adjust the pH to 7.0 at 45°C. When cooled,
The following was observed. Prototype Observations A Opaque Emulsion B Clear Homogeneous Solution C Clear Homogeneous Solution C Opaque Emulsion (b) The following formulations are all examples of cooled mixtures. In all cases, the ingredients were added sequentially with mixing until homogeneous, then the pH was adjusted to 7.0 with citric acid. In all these cases the amount of polyquaternary compound corresponded to 1.0% active substance.

【table】

[Table] Sodium acid

【table】

Table: Appearance Formulation A - Clear Formulation B - Clear Formulation C - Cloudy Emulsion Formulation D - Separation The above data clearly demonstrate that the use of polyquaternary ammonium components results in considerable improvement in formulations. The quaternary polyamide used in the present invention is Mirapol A.
The quaternary polyamide used in the above formulation was used in Mirapol A-15, as it would be unexpected to one skilled in the art to be more water soluble than a quaternary urea such as Mirapol A-15.
Not only does it have a much higher molecular weight than , but it also has a much higher mass/positive charge ratio, as shown in the following table. Both of these factors were believed to reduce the aqueous solubility of the compounds used in the invention, making it more difficult to produce formulations containing them.

Table: For the user, clear formulations are usually preferable to cloudy emulsions. thus,
The fact that the quaternary polyamides used in the present invention, as described above, facilitate the manufacture of cosmetic compositions represents a step ahead in the art. Example (a) A formulation with the following composition was prepared.

[Table] Igepal CO-630 is a nonionic surfactant manufactured by GAF. This material is an ethoxylated nonylphenol containing on average 9 oxyethylene groups per molecule. Mirapol AD-1 is the product corresponding to Example IB. Mirapol A-15 is patented by Christiansen US Patent No. 4157388.
The quaternary polyurea product according to No. Four panelists tested these formulations for use as conditioning shampoos. The results are as follows. Three out of four people reported that Formulation A provided better wet and dry combability and non-tangle properties than Formulation B. All panelists reported that Formulation A provided excellent texture to the hair. This was not seen with Formulation B. The above results are better than those of Christian Jensen.
The advantages of the products of the invention are clearly demonstrated, especially in formulations free of anionic surfactants.

Claims (1)

[Claims] 1. A polyquaternary ammonium polymer having a number average molecular weight of at least 20,000 represented by the following formula: (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, hydrogen, methyl, ethyl,
Propyl, _-CH2CH2OH , _{-CH2CH (} OH) _CH3 ,
and _-CH2CH2 ( _{OCH2CH2 ) pOH} , where p is 0 or an integer from 1 to 6, and _R1 , _R2 , _R3 , and _{R4 are} cannot represent hydrogen at the same time; x and y may be the same or different and are integers from 1 to 6; n is the number of repeating units; m is an integer from 1 to 34; and Z is a halogen or an amino-diamidammonium residue of the formula: (where R ₁ , R ₂ , R ₃ , R ₄ , and m are the same as above). 2. Polymer according to claim 1, wherein m is 4 and x is 3. 3. A cosmetic composition comprising a suitable cosmetic carrier and a polyquaternary ammonium polymer represented by the following formula: (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, hydrogen, methyl, ethyl,
Propyl, _-CH2CH2OH , _{-CH2CH (} OH) _CH3 ,
and _-CH2CH2 ( _{OCH2CH2 ) pOH} , where p is 0 or an integer from 1 to 6, and _R1 , _R2 , _R3 , and _{R4 are} cannot represent hydrogen at the same time; x and y may be the same or different and are integers from 1 to 6; n is the number of repeating units; m is an integer from 1 to 34; and Z is a halogen or an amino-diamidammonium residue of the formula: (where R ₁ , R ₂ , R ₃ , R ₄ , and m are the same as above). 4. The composition of claim 3, wherein m is 4 or 7, and x and y are each 3. 5. The composition according to claim 3 or 4, wherein the cosmetic carrier is a carrier for use in hair formulations. 6. The composition according to claim 5, wherein the hair preparation is shampoo. 7 Claims 3 or 4, wherein the cosmetic carrier is a carrier for use in skin care products.
The composition described in Section. 8. The composition of claim 7, wherein the skin care product is a soap.